Morphology of cold-drawn polyethylene

Small-angle studies suggest the presence of either a 1000- or a 100-Å periodicity in cold-drawn polyethylene. A 1000-Å periodicity is shown in cold-drawn polyethylene thin films to be due to regular placements of portions of two or three lamellae which stayed together during deformation by interlamellar ties. The 100-Å periodicity is shown by dark-field electron microscopy and, in particular, by bright-field diffraction-contrast microscopy to be due to alternating crystalline and noncrystalline units aligned in 100-Å diameter microfibrils. At lower draw ratios, a lateral alignment of the 100-Å units is observed, resulting in the formation of “wavy lamellae.” Although the wavy lamellae are destroyed at higher draw ratios, the 100-Å units remain present throughout the sample. These observations suggest the possible presence of a grain structure of the order of 100 Å in the original crystal.     

Superlattices of lamellae in microporous oriented polyolefine films

The structure and mechanism of the formation of superlattices lamellae in microporous polyolefine (polyethylene and polypropylene) films obtained by polymer melt extrusion followed by annealing, uniaxial extension, and thermal fixation stages have been studied by scanning electron and atomic-force microscopy. It has been shown that oriented anisometric particles, i.e., lamellae aggregates, are formed in films as the spin draw ratio λ _f increases. At the stage of uniaxial extension (pore formation) of annealed films, a particle ensemble transforms to spatial superlattices of lamellae. Numerical processing of electron microscopy images of the film surface show that the nonmonotonic dependences of the correlation length of density fluctuations and the ratios of the alternation period of particles along extension to their thickness on the parameter λ _f correspond to a unified mechanism of lamellae ordering.     

Deformation and annealing behavior. III. thin films of polycarbonate,isotactic polymethyl methacrylate,and isotactic polystyrene

The morphology of thin films of polycarbonate (PC), isotactic polymethyl methacrylate (i-PMMA), and isotactic polystyrene (i-PS) were studied by bright field, diffraction, and dark field transmission, electron microscopy. The films were thermally annealed both before and after uniaxial deformation. The undrawn i-PMMA did not develop a crystalline texture upon annealing whereas the undrawn i-PS developed a random arrangement of lamellae. Thermal crystallization of undrawn PC has been shown to occur through the growth and merging of a nodular structure into fibrillar spherulites. Deformation of gold-decorated samples indicated a nonhomogeneous structure in the amorphous polymer on the 200-500 A scale. Thermal annealing of drawn samples resulted in fibrillar lamellae arranged perpendicular to the draw direction for all three polymers, indicating the straining has a marked influence on the crystalline morphology. This morphology is compared to similar morphologies reported in the literature for crystallization from stressed melts. High-resolution dark field micrographs confirm this morphology and indicate variations in crystallite size, depending upon the polymer and deformation conditions.     

Length scale effect on the deformation microstructures of grown-in twins in copper

Electrodeposited copper samples composed of columnar grains subdivided by alternating twin/matrix (T/M) lamellae have been cold rolled to 30–85% reduction in thickness. The thickness of the T/M lamellae varies over a wide range from a few nanometres to about 1?μm. The deformation microstructure has been characterized systematically. In thin T/M lamellae (below 50–100?nm) the deformation behaviours differ significantly from that of thick T/M lamellae, as the dislocation activity is concentrated at the T/M boundaries illustrated by the observations of stacking faults and Shockley partial dislocations. In thick T/M lamellae (100–1000?nm), the deformation microstructure is related to the grain orientation as also observed previously in deformed single crystals and polycrystals with a grain size at the micrometre scale. The experiment therefore suggests that the universal structural characteristics of deformation microstructure can be extended one order of magnitude from about 5?μm to the sub-micrometre scale (about 0.5?μm).     

Hard elastic fibers. II. Destructible and indestructible microparacrystals and their importance for understanding the properties of hard elastic fibers

A new structural model is introduced for hard elastic fibers based on nuclear magnetic resonance measurements and supplemented by known facts about the structure of nonelastic meltcrystallized polymers, electron micrographs of 300 A thick hard elastic films, and carlorimetric deformation results. The microparacrystals (mPC's) build up perfectly regular lamellae, the distances between which increase uniformly during straining. This is explained by a three-dimensional network which is relatively weak compared with the stiffness of the lamellae. Only the mPC's at the lamellar ends can be destroyed under stress (dmPC's). Their large free surface produces the reverse driving forces. Exothermal effects during straining can be partially explained by the heat of gas adsorption at these newly generated free surfaces. The destructible mPC's are the elastic tie-points between adjacent lamellae and correspond to the taut connection between leaf springs and the oriented chains in the models of Noether et al. and Gdritz and Müller.     

Cyclic deformation of polycrystalline Cu films

Fatigue impairs the reliability of macroscopic metallic components utilized in a variety of technological applications. However, the fatigue behaviour of thin metal films and small-scale components used in microelectronics and mechanical microdevices has yet to be explored in detail. The fatigue behaviour in submicrometre thin films is likely to differ from that in bulk material, since the volume necessary for the formation of dislocation structures typical of cyclic deformation in bulk material is larger than that available in thin films. The thin-film dimensions and microstructure, therefore, affect the microscopic processes responsible for fatigue. The fatigue behaviour of Cu films 0.4, 0.8 and 3.0 µm thick on polyimide substrates was investigated. The specimens were fatigued at a total strain amplitude of 0.5% using an electromechanical tensile-testing machine. This work focuses on the characterization of fatigue mechanisms and the resulting fatigue damage of thin Cu films. Extrusions similar to those observed in bulk material were found at the film surfaces after cyclic loading. Voids observed beneath the extrusions, close to the film-substrate interface, contributed significantly to thin-film failure. Thinner films were more fatigue resistant and contained fewer and smaller extrusions than thicker films did. A small thickness appears to inhibit void nucleation. This observation is explained in terms of vacancy diffusion and annihilation at free surfaces or grain boundaries. Transmission electron microscopy investigations confirmed that no long-range dislocation structures have developed during fatigue loading of the films investigated.     

Regularities of lamellae ordering in the formation of polypropylene membrane porous structure

The lamellar structure of porous polypropylene membranes prepared by the extrusion of the polymer melt, annealing of extruded films, and their uniaxial extension has been investigated using data of computer analysis of scanning electron microscopy images. It has been shown that the formation of pores at the stage of uniaxial extension is accompanied by an ordering of lamellae or their self-organization controlled by the annealing temperature T _ann. It has been found that the self-organization of lamellae can occur through two mechanisms depending on the spin draw ratio at the stage of extrusion of the polymer melt: in the first case, an increase in the temperature T _ann leads to a gradual transition of the disorder-order type; in the second case, a bifurcation transition occurs with a nonmonotonic change in the order parameter. The conditions of the preparation of regular spatial lattices of lamellae have been discussed.     

Deformation and annealing behavior. II. Thick polyethylene terephthalate films

Thick (5-30 mil) samples of polyethylene terephthalate (PET), drawn uniaxially and biaxially followed by thermal crystallization, were studied by replication electron microscopy and wide- and small-angle X-rays. Deformation of gold-decorated samples indicated that aggregates on the 200–500 Å scale move as units during deformation. Thermal crystallization of both uniaxially and biaxially drawn samples occurred with the formation of coarse 200–500 Å nodular aggregates, which, in turn, may consist of the 75–100 Å nodules observed by Yeh and Geil. At annealing temperatures above 180° C, fibrillar lamellae are formed, arranged perpendicular to the draw direction in uniaxially drawn samples and at random in biaxially drawn samples. Small-angle photographs and pole figures of uniaxially drawn and annealed samples can be explained in terms of a toroidal arrangement of poles centered about the draw direction.     

Morphologies of diblock copolymer thin films before and after crystallization

Spin-coated thin films of about 100nm of low-molecular-weight hydrogenated poly(butadiene-b- ethyleneoxide) (PB_h-PEO) diblock copolymers have been crystallized at various constant temperatures. Crystallization has been observed in real time by light microscopy. Detailed structural information was obtained by atomic force microscopy, mainly enabled by the large viscoelastic contrast between amorphous and crystalline regions. The behavior in thin films is compared to the bulk properties of the polymer. Crystallization started from an annealed microphase separated melt where optical microscopy indicated a lamellar orientation parallel to the substrate. A small difference in the length of the crystallizable block produced significantly different crystallization behavior, both in the bulk and in thin films. For thin films of the shortest diblock copolymer (45% PEO content) and for an undercooling larger than about 10 degrees, crystallization created vertically oriented lamellae. These vertical lamellae could be preferentially aligned over several micrometers when crystallization occurred close to a three-phase contact line. Annealing at temperatures closer to the melting point or keeping the sample at room temperature for several months allowed the formation of a lamellar structure parallel to the substrate. A tentative interpretation based on kinetically caused chain folding and relaxation within the crystalline state, with implications on general aspects of polymer crystallization, is presented. Received 19 March 1999 and Received in final form 14 December 1999     

Mechanism of spherulitic crystallization as deduced from observations of partially crystallized glassy polystyrene

Thin films of isotactic polystyrene partially crystallized from the glassy state were studied in detail by means of transmission electron microscopy and electron diffraction. Initial nucleation and growth stages of spherulitic fibrils (or lamellae) were illustrated clearly by using novel techniques, such as Au decoration, and novel specimens such as thin films containing holes.

Spherulitic nucleation begins with the crystallization of a liquid-crystal-like nodule or a group of these nodules merging to form a spherulitic center. Fibrils or lamellae grow and fan out from the nucleus by additional incorporation of maturing nodules. Proliferation of fibrils is essentially a space-filling process through the crystallization of uncrystallized nodules or nodules that were left behind by growing fibrils which had initiated earlier. The deduced mechanism of spherulitic crystallization leads directly to the formation of interlamellar links between neighboring fibrils. However, no extended-chain-type interlamellar links were revealed by Au decoration.

The application of the mechanism of spherulitic crystallization from the glass to that from the melt is also suggested; it is based primarily on recent studies which show remarkable similarities between structures existing in the glassy and the melt states prior to crystallization.     

Enhancing nucleation and controlling crystal orientation by rubbing/scratching the surface of a thin polymer film

We used the tip of an atomic force microscope (AFM) in the contact mode to scratch/rub the surface of a glassy polymer thin film, i.e., isotactic polystyrene (i-PS) at room temperature. After subsequent isothermal crystallization, an extremely high nucleation density of edge-on crystals within the rubbed region or at the edge of the scratched area was observed. Furthermore, a transition from edge-on to flat-on lamellae occurred beyond a certain distance from the edge of the scratched region. Our results demonstrate that both, soft rubbing or hard scratching, allow to lower the nucleation barrier for polymer crystallization and to control the orientation of the resulting crystalline lamellae. The role of scratching/rubbing on chain deformation and its relation to nucleation and crystal orientation in polymer thin films is discussed.     

Selective electroplating of copper lines on pre-patterned tantalum oxide thin films

Direct selective metal deposition on semiconductors is of interest to electronic device technology, in particular for interconnects and Schottky devices. In this study, we investigate selective copper electrodeposition on patterned tantalum oxide thin films. Cyclic voltammetry studies show that thick tantalum oxide thin films have insulating properties while oxide films thinner than a critical value are semiconductors. Copper films electrodeposited on tantalum oxide thin films are known to form Schottky contacts. We demonstrate the formation of copper patterns on pre-patterned tantalum oxide films by a simple process: an insulating tantalum oxide film was grown electrochemically, the film was then mechanically scratched followed by mild oxidation to produce a thin tantalum oxide film inside the scratch. Based on the differential behavior of thin and thick tantalum oxide films, metal lines were electrodeposited selectively under formation of Schottky junctions. The process demonstrated in this paper is compatible to standard processes for semiconductor device fabrication while permitting flexible prototyping for research at small scales.     

C60 adsorption on Cu(110) studied by optical spectroscopy

The formation of the interface between C₆₀ thin films and the Cu(110) surface has been investigated in situ using reflectance difference spectroscopy (RDS). The electronic interaction between C₆₀ molecules in the first monolayer and the substrate inhibits low‐energy intramolecular transitions, whereas the C₆₀ molecules above the first monolayer are effectively decoupled from the substrate. The morphology of C₆₀ thin films prepared at room temperature is thermally stable up to 500 K. Above this threshold, optical spectroscopy and low energy electron diffraction (LEED) indicate the formation of rather large three dimensional C₆₀ islands on a one monolayer thick wetting layer. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Synthesis and characterization of (h 0 h)-oriented silicalite-1 films on α-Al2O3 substrates

A simple and well-designed synthesis procedure is proposed to fabricate silicalite-1 films on porous α-Al₂O₃ substrates on purpose of preventing the aluminum leaching. The continuous and 2 μm thick seed layer of silicalite-1 crystals is fabricated by using a spin coater. The first-time seeded growth is performed to synthesize a thin layer of intergrown ZSM-5 crystals on the silicalite-1 seed layer, where the use of low alkalinity and short synthesis time is to reduce the aluminum leaching. The intergrown layer of ZSM-5 crystals serves as a barrier to block the aluminum leaching from porous α-Al₂O₃ substrates in the second-time seeded growth, leading to the formation of ca. 11 μm thick intergrown and oriented silicalite-1 films with an extremely high Si/Al ratio. According to SEM images and XRD measurements, the as-synthesized silicalite-1 film is dense, continuous, and (1 0 1)-oriented. The electron probe microanalysis (EPMA) of the resulting film demonstrates that there is no aluminum leaching in the second-time seeded growth. The leaking tests confirm that non-zeolitic pores in the silicalite-1 film are negligible.     

Collagen fibril formation in poly(vinyl alcohol) and poly(vinyl pyrrolidone) films

The formation of collagen fibrils in poly(vinyl alcohol) (PVA) and in poly(vinyl pyrrolidone) (PVP) was investigated using Atomic Force Microscopy (AFM). The water solutions of PVA and PVP containing 1%, 3% and 5% of collagen were cast onto glass plate. After slow solvent evaporation thin polymeric films were obtained. AFM images showed the fibril formation in both, PVA and PVP films containing collagen. The amount of collagen in PVA and PVP matrix has an important effect on the structure and size of collagen fibril formed. The diameter of collagen fibrils in PVA films is bigger than the diameter of collagen fibrils formed in PVP films.     

Mechanism of necking as revealed by ultrasonic cavitation of polyethylene single crystals

Ultrasonic cavitation of polyethylene single crystals and single-crystal aggregates in the form of cakes results in lamella fragmentation and necking involving the transformation of lamellar crystals into fibrillar crystals between 20 to 400 Å in diameter. The smaller fibrils (～20–30 Å) have a very smooth appearance, whereas the larger ones (～100–400 Å) contain a beady structure about 100 Å periodically spaced along the fibrils. The smoother microfibrils are suggested to contain extended chains that are formed by unfolding of molecules directly from the chain-folded lamellae as well as from the folded-chain crystals contained within the beady fibrils. The presence of the chain-folded crystals within the larger beady fibrils is shown in numerous instances to be due to incorporation of mosaic crystalline blocks originally present, but weakly connected to one another, in the lamellar single crystals. The necking process is deduced by observation to involve primarily a mechanical shearing of mosaic crystalline blocks along the c-axis plus a rotation into the fibril direction. Observation of extreme resistance of lamellae in the overgrowth regions to cavitation damage suggests the presence of tie molecules and/or interpenetrating cilia between these lamellae. The suggestion finds strong support from additional studies carried out on lamellae that have been tied together at the folds by cross-linking with γ rays.     

Microstructural evolution of AZ31 magnesium alloy subjected to sliding friction treatment

Microstructural evolution and grain refinement mechanism in AZ31 magnesium alloy subjected to sliding friction treatment were investigated by means of transmission electron microscopy. The process of grain refinement was found to involve the following stages: (I) coarse grains were divided into fine twin plates through mechanical twinning; then the twin plates were transformed to lamellae with the accumulation of residual dislocations at the twin boundaries; (II) the lamellae were separated into subgrains with increasing grain boundary misorientation and evolution of high angle boundaries into random boundaries by continuous dynamic recrystallisation (cDRX); (III) the formation of nanograins. The mechanisms for the final stage, the formation of nanograins, can be classified into three types: (i) cDRX; (ii) discontinuous dynamic recrystallisation (dDRX); (iii) a combined mechanism of prior shear-band and subsequent dDRX. Stored strain energy plays an important role in determining deformation mechanisms during plastic deformation.     

A new chemical bath deposition method for fabricating ZnS,Zn(OH)<Subscript>2</Subscript>, and ZnO thin films,and the optical and structural characterization of these materials

ZnS thin films were deposited on glass and polymer substrates using a reaction between thiourea and a stable zinc complex, Zn(en)₃SO₄ (en: ethylenediamine) or Zn(trien)(ClO₄)₂ (trien: triethylenetetraamine), in alkaline media. In a weak alkaline solution, Zn(OH)₂ films were formed. The deposition reactions were controlled by the supply of sulfide ions from thiourea at a suitable rate in alkaline media and by the dissociation of free-metal ions from the metal complex used, the stability of which defined the free Zn²⁺ concentration throughout the reaction. The ZnS films showed emission peaks at ca. 450 and 485 nm, and the transmittance decreased with decreasing wavelength of the incident light in the visible region of the spectrum. ZnO thin films were deposited by decomposition of Zn(en)₃SO₄ in the presence of Cu(en)₂(ClO₄)₂ and thiourea; the copper(II) complex catalyzes this reaction. The ZnO films exhibited an emission peak at ca. 420 nm, and the absorbance was constant in the visible region of the spectrum. The scanning electron microscope images showed the formation of a fairly uniform surface with fine crystalline particles. PACS 81.15.-z; 68.55.-a; 81.05.Dz     

Solid-state 13C NMR and synchrotron SAXS/WAXS studies of uniaxially-oriented polyethylene

We report solid-state ¹³C NMR and synchrotron wide-and small-angle X-ray scattering experiments (WAXS, SAXS) on metallocene linear low density polyethylene films (e.g., Exceed™ 1018 mLLDPE; nominally 1 MI, 0.918 density ethylene-hexene metallocene copolymer) as a function of uniaxial draw ratio, λ. Combined, these experiments provide an unambiguous, quantitative molecular view of the orientation of both the crystalline and amorphous phases in the samples as a function of draw. Together with previously reported differential scanning calorimetry (DSC), gas transport measurements, transmission electron microscopy (TEM), optical birefringence, small angle X-ray scattering (SAXS) as well as other characterization techniques, this study of the state of orientation in both phases provides insight concerning the development of unusually high barrier properties of the most oriented samples (λ=10). In this work, static (non-spinning) solid-state NMR measurements indicate that in the drawn Exceed^TM films both the crystalline and amorphous regions are highly oriented. In particular, chemical shift data show the amorphous phase is comprised increasingly of so-called “taut tie chains” (or tie chains under any state of tautness) in the mLLDPE with increasing draw ratio – the resonance lines associated with the amorphous phase shift to where the crystalline peaks are observed. In the sample with highest total draw (λ=10), virtually all of the chains in the non-crystalline region have responded and aligned in the machine (draw) direction. Both monoclinic and orthorhombic crystalline peaks are observed in high-resolution, solid-state magic-angle spinning (MAS) NMR measurements of the oriented PE films. The orientation is comparable to that obtained for ultra-high molecular weight HDPE fibers described as “ultra-oriented” in the literature. Furthermore, the presence of a monoclinic peak in cold-drawn samples suggests that there is an appreciable internal stress associated with the LLDPE. The results are confirmed and independently quantified by Herman's Orientation Function values derived from the WAXS measurements. The degree of orientation approaches theoretically perfect alignment of chains along the draw direction. We deduce from this observation that a high fraction of the non-crystalline chains are either tie chains that directly connect adjacent lamellae or are interlocking loops from adjacent lamellae. In either case, the chains are load-bearing and are consistent with the idea of “taut tie chains”. We note that transmission electron micrographs recorded for the ultra-oriented Exceed showed the lamellae are often appreciably thinner and shorter than they are for cast or blown Exceed 1018. Combined with higher crystallinity, the thinner lamellae statistically favor more tie chains. Finally, the remarkably large decrease in permeability of the λ=10 film is primarily attributed to the high degree of orientation (and loss of entropy) of the amorphous phase.     

Layer-by-layer epitaxial growth of polar FeO(111) thin films on MgO(111)

We report on the structural properties of epitaxial FeO layers grown by molecular beam epitaxy on MgO(111). The successful stabilization of polar FeO films as thick as 16 monolayers (ML), obtained by deposition and subsequent oxidation of single Fe layers, is presented. FeO/MgO(111) thin films were chemically and structurally characterized using low-energy electron diffraction, Auger electron spectroscopy and conversion electron Mössbauer spectroscopy (CEMS). Detailed in situ CEMS measurements as a function of the film thickness demonstrated a size-effect-induced evolution of the hyperfine parameters, with the thickest film exhibiting the bulk-wüstite hyperfine pattern. Ex situ CEMS investigation confirmed existence of magnetic ordering of the wüstite thin film phase at liquid nitrogen temperature.